Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled (NO)-N-15 over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H2 and/or CO and NO on reduced Rh and/or Pt sites. The second N2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H2.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.

Electroreduction of oxygen in a series of room temperature ionic liquids composed of group 15-centered cations and anions

The electrochemical reduction of oxygen is reported in four room temperature ionic liquids (RTILs) based on quaternary alkyl -onium cations and heavily fluorinated anions in which the central atom is either nitrogen or phosphorus. Data were collected using cyclic voltammetry and potential step chronoamperometry at gold, platinum, and glassy carbon disk electrodes of micrometer dimension under water-free conditions at a controlled temperature. Analysis via fitting, to appropriate theoretical equations was then carried out to obtain kinetic and thermodynamic information pertaining to the electrochemical processes observed. In the quaternary ammonium electrolytes, reduction of oxygen was found to occur reversibly to give stable superoxide, in an analogous manner to that seen in conventional aprotic solvents such as dimethyl sufoxide and acetonitrile. The most significant difference is in the relative rate of diffusion; the diffusion coefficients of oxygen in the RTILs are an order of magnitude lower than in common organic solvents, and for superoxide these values are reduced by a further factor of 10. In the quaternary phosphonium ionic liquids, however, more complex voltammetry is observed, akin to that expected for the reduction of oxygen in acidified organic media. This is shown to be consistent with the occurrence of a proton abstraction reaction between the electrogenerated superoxide and quaternary alkyl phosphonium cations following the initial electron transfer.

The massive neutron star or low-mass black hole in 2S 0921-630

We report on the optical spectroscopy of the eclipsing halo low-mass X-ray binary 2S 0921-630, which reveals the absorption-line radial velocity curve of the K0 III secondary star with a semiamplitude K-2=92.89+/-3.84 km s(-1), a systemic velocity gamma=34.9+/-3.3 km s(-1), and an orbital period P-orb of 9.0035+/-0.0029 days (1 sigma). Given the quality of the data, we find no evidence for the effects of X-ray irradiation. Using the previously determined rotational broadening of the mass donor and applying conservative limits on the orbital inclination, we constrain the compact object mass to be 2.0-4.3 M-circle dot (1 sigma), ruling out a canonical neutron star at the 99% level. Since the nature of the compact object is unclear, this mass range implies that the compact object is either a low-mass black hole with a mass slightly higher than the maximum possible neutron star mass (2.9 M-circle dot) or a massive neutron star. If the compact object is a black hole, it confirms the prediction of the existence of low-mass black holes, while if the object is a massive neutron star, its high mass severely constrains the equation of state of nuclear matter.

Community Regeneration: An Elite or a ‘Real’ Community Space?

Identifying community interests in the processes of planning and regeneration is less than straightforward. By their very nature programmes encourage the development of particular projects, typically relying on experience from past initiatives to inform current practice. One of the difficulties for partners is juggling the need to comply with administrative demands while engaging in a meaningful way with their community. This article uses empirical evidence to examine power relations within structures of governance. It argues that current processes are unable to identify real community interests and consequently create space that favour elite interests, all of which restrain the impact of governance.

Mandelohydroxamic acid as ligand for copper(II) 15-metallacrown-5 lanthanide(III) and copper(II) 15-metallacrown-5 uranyl complexes

The formation of pentanuclear copper(ii) complexes with the mandelohydroxamic ligand was studied in solution by electrospray ionization mass spectrometry (ESI-MS), absorption spectrophotometry, circular dichroism and H-1 NMR spectroscopy. The presence of lanthanide(iii) or uranyl ions is essential for the self-assembly of the 15-metallacrown-5 compounds. The negative mode ESI-MS spectra of solutions containing copper(II), mandelohydroxamic acid and lanthanide(iii) ions (Ln = La, Ce, Nd, Eu, Gd, Dy, Er, Tm, Lu, Y) or uranyl in the ratio 5:5:1 showed only the peaks that could be unambiguously assigned to the following intact molecular ions: {Ln(NO3)(2)[15-MCuIIN(MHA)-5](2-)}(-) and {Ln(NO3)[15-MCCuIIN(MHA)-5](3-)}(-), where MHA represents doubly deprotonated mandelohydroxamic acid. The NMR spectra of the pentanuclear species revealed only one set of peaks indicating a fivefold symmetry of the complex. The pentanuclear complexes synthesized with the enantiomerically pure R- or S-forms of mandelohydroxamic acid ligand, showed circular dichroism spectra which were mirror images of each other. The pentanuclear complex made from the racemic form of the ligand showed no signals in the CD spectrum. The UV/ Vis titration experiments revealed that the order in which the metal salts are added to the solution of the mandelohydroxamic acid ligand is crucial for the formation of metallacrown complexes. The addition of copper(ii) to the solutions containing mandelohydroxamic acid and neodymium(iii) in a 5:1 ratio lead to the formation of a pentanuclear complex in solution. In contrary, titration of lanthanide(iii) salt to the solution containing copper(ii) and mandelohydroxamic acid did not show any evidence for the formation of pentanuclear species. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Ionic Liquid-Based Routes to Conversion or Reuse of Recycled Ammonium Perchlorate

New, potentially green, and efficient synthetic routes for the remediation and/or re-use of perchlorate-based energetic materials have been developed. Four simple organic imidazolium- and phosphonium-based perchlorate salts/ionic liquids have been synthesized by simple, inexpensive, and nonhazardous methods, using ammonium perchlorate as the perchlorate source. By appropriate choice of the cation, perchlorate can be incorporated into an ionic liquid which serves as its own electrolyte for the electrochemical reduction of the perchlorate anion, allowing for the regeneration of the chloride-based parent ionic liquid. The electrochemical degradation of the hazardous perchlorate ion and its conversion to harmless chloride during electrolysis was studied using IR and Cl-35 NMR spectroscopies.

delta C-13 and delta N-15 reveal significant differences in the coastal foodwebs of the seas surrounding Trinidad and Tobago

This study assessed nearshore, marine ecosystem function around Trinidad and Tobago (TT). The coastline of TT is highly complex, bordered by the Atlantic Ocean, the Caribbean Sea, the Gulf of Paria and the Columbus Channel, and subject to local terrestrial runoff and regional riverine inputs (e.g. the Orinoco and Amazon rivers). Coastal organisms can assimilate energy from allochthonous and autochthonous Sources, We assessed whether stable isotopes delta C-13 and delta N-15 Could be used to provide a rapid assessment of trophic interactions in primary consumers around the islands. Filter-feeding (bivalves and barnacles) and grazing organisms (gastropods and chitons) were collected from 40 marine sites during the wet season. The flesh of organisms was analysed for delta C-13 and delta N-15. Results indicate significant variation in primary consumers (by feeding guild and sampling zone). This variation was linked to different energy Sources being assimilated by consumers. Results suggest that offshore production is fuelling intertidal foodwebs; for example, a depleted delta C-13 signature in grazers from the Gulf of Paria, Columbus Channel and the Caribbean and Atlantic coastline of 9 Tobago indicates that carbon with an offshore origin (e.g. phytoplankton and dissolved organic matter) is more important than benthic or littoral algae (luring the wet season. Results also confirm findings from other studies indicating that much of the coastline is subject to Cultural eutrophication. This Study revealed that ecosystem function is spatially variable around the coastline of TT, This has clear implications for marine resource management, as a single management approach is unlikely to be successful at a national level.

Management of varicella contacts in pregnancy: VZIG or Vaccination?

Background Varicella infection during pregnancy poses a serious risk for both foetus and mother. It has been suggested that it would be more cost-effective to screen antenatally with post-partum vaccination, which occurs in the US, than the current policy of checking immune status post varicella exposure, with VZIG administration where necessary. Additionally, it is doubtful whether the current policy provides best patient care, when a vaccine is available. Objectives The study aims to retrospectively compare the cost of the current policy with a cost estimate for antenatal screening with post-partum vaccination in NI. Study design A cost estimate of antenatal screening of primigravidas, with post-partum vaccination, was calculated for two models: (1) verbal screening, with serological testing of those with no history of varicella infection and (2) serological screening of all primigravidas. Results The cost of VZIG issued to pregnant women in 2006 was £100,800; 43% of births were to primigravidas therefore the estimated cost of VZIG issued to multigravidas was £58,100. The cost of verbal screening with post-partum vaccination is estimated at £23,750 p.a., saving £34,350 over current policy. The estimated cost of screening all primigravidas with post-partum vaccination is £43,000, saving £15,100. Conclusions This retrospective study suggests that in NI either of the proposed antenatal screening strategies would be less costly than current practice. This finding supports the suggestion that varicella immunity testing should be included in the Antenatal Infectious Diseases Screening Programme, either as part of the universal vaccination programme or solely as an antenatal programme.

Acoustic solitary waves in dusty and/or multi-ion plasmas with cold, adiabatic, and hot constituents

Large nonlinear acoustic waves are discussed in a four-component plasma, made up of two superhot isothermal species, and two species with lower thermal velocities, being, respectively, adiabatic and cold. First a model is considered in which the isothermal species are electrons and ions, while the cooler species are positive and/or negative dust. Using a Sagdeev pseudopotential formalism, large dust-acoustic structures have been studied in a systematic way, to delimit the compositional parameter space in which they can be found, without restrictions on the charges and masses of the dust species and their charge signs. Solitary waves can only occur for nonlinear structure velocities smaller than the adiabatic dust thermal velocity, leading to a novel dust-acoustic-like mode based on the interplay between the two dust species. If the cold and adiabatic dust are oppositely charged, only solitary waves exist, having the polarity of the cold dust, their parameter range being limited by infinite compression of the cold dust. However, when the charges of the cold and adiabatic species have the same sign, solitary structures are limited for increasing Mach numbers successively by infinite cold dust compression, by encountering the adiabatic dust sonic point, and by the occurrence of double layers. The latter have, for smaller Mach numbers, the same polarity as the charged dust, but switch at the high Mach number end to the opposite polarity. Typical Sagdeev pseudopotentials and solitary wave profiles have been presented. Finally, the analysis has nowhere used the assumption that the dust would be much more massive than the ions and hence, one or both dust species can easily be replaced by positive and/or negative ions and the conclusions will apply to that plasma model equally well. This would cover a number of different scenarios, such as, for example, very hot electrons and ions, together with a mix of adiabatic ions and dust (of either polarity) or a very hot electron-positron mix, together with a two-ion mix or together with adiabatic ions and cold dust (both of either charge sign), to name but some of the possible plasma compositions.

CD18-dependent activation of the neutrophil NADPH oxidase during phagocytosis of Escherichia coli or Staphylococcus aureus is regulated by class III but not class I or II PI3Ks

Phagocytosis and activation of the NADPH oxidase are important mechanisms by which neutrophils and macrophages engulf and kill microbial pathogens. We investigated the role of PI3K signaling pathways in the regulation of the oxidase during phagocytosis of Staphylococcus aureus and Escherichia coli by mouse and human neutrophils, a mouse macrophage-like cell line and a human myeloid-like cell line. Phagocytosis of these bacteria was promoted by serum, independent of serum-derived antibodies, and effectively abolished in mouse neutrophils lacking the beta(2)-integrin common chain, CD18. A combination of PI3K isoform-selective inhibitors, mouse knock-outs, and RNA-interference indicated CD18-dependent activation of the oxidase was independent of class I and II PI3Ks, but substantially dependent on the single class III isoform (Vps34). Class III PI3K was responsible for the synthesis of PtdIns( 3) P on phagosomes containing either bacteria. The use of mouse neutrophils carrying an appropriate knock-in mutation indicated that PtdIns(3) P binding to the PX domain of their p40(phox) oxidase subunit is important for oxidase activation in response to both S aureus and E coli. This interaction does not, however, account for all the PI3K sensitivity of these responses, particularly the oxidase response to E coli, suggesting that additional mechanisms for PtdIns( 3) P-regulation of the oxidase must exist. ( Blood. 2008; 112: 5202-5211)

A 'Teague' and a 'True Briton': Charles Johnstone, Ireland, and Empire

Charles Johnstone's literary output - which included Chrysal: or, the Adventures of a Guinea (1760) and a series of novels between 1762 and 1781 prior to his departure for Calcutta in 1782 - features a marked geographical and historical preoccupation with empire. The trajectory of Johnstone's life from Carrigogunnell and Dublin in Ireland, to London, and finally to Calcutta, indicates the remarkable possibilities for self-transformation which empire from Ireland to India offered during the eighteenth century. This paper examines the significance of empire in Johnstone's oeuvre, and identifies for the first time a series of articles written by him in The Calcutta Gazette in 1785.

Evidence of association of APOE with age-related macular degeneration: a pooled analysis of 15 studies.

Age-related macular degeneration (AMD) is the most common cause of incurable visual impairment in high-income countries. Previous studies report inconsistent associations between AMD and apolipoprotein E (APOE), a lipid transport protein involved in low-density cholesterol modulation. Potential interaction between APOE and sex, and smoking status has been reported. We present a pooled analysis (n = 21,160) demonstrating associations between late AMD and APOe4 (odds ratio [OR] = 0.72 per haplotype; confidence interval [CI]: 0.65-0.74; P = 4.41×10(-11) ) and APOe2 (OR = 1.83 for homozygote carriers; CI: 1.04-3.23; P = 0.04), following adjustment for age group and sex within each study and smoking status. No evidence of interaction between APOE and sex or smoking was found. Ever smokers had significant increased risk relative to never smokers for both neovascular (OR = 1.54; CI: 1.38-1.72; P = 2.8×10(-15) ) and atrophic (OR = 1.38; CI: 1.18-1.61; P = 3.37×10(-5) ) AMD but not early AMD (OR = 0.94; CI: 0.86-1.03; P = 0.16), implicating smoking as a major contributing factor to disease progression from early signs to the visually disabling late forms. Extended haplotype analysis incorporating rs405509 did not identify additional risks beyond e2 and e4 haplotypes. Our expanded analysis substantially improves our understanding of the association between the APOE locus and AMD. It further provides evidence supporting the role of cholesterol modulation, and low-density cholesterol specifically, in AMD disease etiology.

Diabetic retinopathy: quantitative variation in capillary basement membrane thickening in arterial or venous environments

Diabetes mellitus was induced in male beagles by a single injection of an alloxan and streptozotocin cocktail and fasting blood sugar levels maintained between 15 and 20 mmol/l. Five years after induction of diabetes, three diabetic animals were sacrificed, together with sex and age-matched controls, and the retinas fixed for either transmission electron microscopy (TEM) or trypsin digestion. In TEM specimens, capillaries in close proximity to the major vessels were designated as either AE (arterial environment) or VE (venous environment) and the thickness of their basement membranes (BMs) measured using an image analyser based two dimensional morphometric analysis system. Results show that the BMs of retinal capillaries from the diabetic dogs were significantly thicker than those from control dogs. Furthermore, within the diabetic group the AE capillaries had thicker BMs than VE capillaries (p less than or equal to 0.05). The controls, however, showed no significant difference in BM thickness between AE and VE capillaries. Although many of the capillaries designated as AE or VE would actually have been derived from the opposite side of the circulation, with respect to BM thickness, they conformed to values of their specific group. The conclusion is that diabetic capillaries are more vulnerable to BM thickening in an arterial environment than in a venous environment.